CN114929661A - Process for preparing alpha-substituted acrylic acid esters - Google Patents
Process for preparing alpha-substituted acrylic acid esters Download PDFInfo
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- CN114929661A CN114929661A CN202080091040.5A CN202080091040A CN114929661A CN 114929661 A CN114929661 A CN 114929661A CN 202080091040 A CN202080091040 A CN 202080091040A CN 114929661 A CN114929661 A CN 114929661A
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- group
- olefin
- ethylene
- propylene
- polymer
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- -1 alpha-substituted acrylic acid Chemical class 0.000 title description 14
- 238000000034 method Methods 0.000 claims abstract description 92
- 150000001875 compounds Chemical class 0.000 claims abstract description 53
- 239000007858 starting material Substances 0.000 claims abstract description 27
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims abstract description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims description 65
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 56
- 239000005977 Ethylene Substances 0.000 claims description 56
- 239000004711 α-olefin Substances 0.000 claims description 47
- 229920000098 polyolefin Chemical group 0.000 claims description 39
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 37
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 37
- 239000003054 catalyst Substances 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 19
- 125000004970 halomethyl group Chemical group 0.000 claims description 11
- 229920002554 vinyl polymer Polymers 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 7
- 229920001519 homopolymer Polymers 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 229920001384 propylene homopolymer Polymers 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical group 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims 1
- 239000000178 monomer Substances 0.000 description 32
- 239000002131 composite material Substances 0.000 description 24
- 229920001400 block copolymer Polymers 0.000 description 18
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 16
- 239000000203 mixture Substances 0.000 description 15
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 14
- 150000001336 alkenes Chemical class 0.000 description 14
- 125000004432 carbon atom Chemical group C* 0.000 description 14
- 238000005227 gel permeation chromatography Methods 0.000 description 14
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 14
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 12
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 10
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 10
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 10
- 238000005481 NMR spectroscopy Methods 0.000 description 10
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 10
- 125000004122 cyclic group Chemical group 0.000 description 9
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 8
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 8
- 239000004793 Polystyrene Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 8
- 229920000573 polyethylene Polymers 0.000 description 8
- 229920002223 polystyrene Polymers 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 4
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 4
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 229940069096 dodecene Drugs 0.000 description 4
- 150000002367 halogens Chemical group 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- 230000000737 periodic effect Effects 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical group ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000004696 coordination complex Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 2
- YWDUZLFWHVQCHY-UHFFFAOYSA-N 1,3,5-tribromobenzene Chemical compound BrC1=CC(Br)=CC(Br)=C1 YWDUZLFWHVQCHY-UHFFFAOYSA-N 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 2
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- 125000006659 (C1-C20) hydrocarbyl group Chemical group 0.000 description 1
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 1
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 description 1
- 229940106006 1-eicosene Drugs 0.000 description 1
- FIKTURVKRGQNQD-UHFFFAOYSA-N 1-eicosene Natural products CCCCCCCCCCCCCCCCCC=CC(O)=O FIKTURVKRGQNQD-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
- PCBPVYHMZBWMAZ-UHFFFAOYSA-N 5-methylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C)CC1C=C2 PCBPVYHMZBWMAZ-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 125000004429 atom Chemical class 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- ZXIJMRYMVAMXQP-UHFFFAOYSA-N cycloheptene Chemical compound C1CCC=CCC1 ZXIJMRYMVAMXQP-UHFFFAOYSA-N 0.000 description 1
- 238000013480 data collection Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 125000004386 diacrylate group Chemical class 0.000 description 1
- 229920000359 diblock copolymer Polymers 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- ZXXGXFJDRGCYKI-UHFFFAOYSA-N dodeca-1,3,5,7,9-pentaene Chemical compound CCC=CC=CC=CC=CC=C ZXXGXFJDRGCYKI-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- MTCMFVTVXAOHNQ-UHFFFAOYSA-N ethyl 2-(bromomethyl)prop-2-enoate Chemical compound CCOC(=O)C(=C)CBr MTCMFVTVXAOHNQ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- MJFYKGUKOYPESV-UHFFFAOYSA-N methyl 3-chloro-2-methylprop-2-enoate Chemical compound COC(=O)C(C)=CCl MJFYKGUKOYPESV-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 238000010653 organometallic reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920005638 polyethylene monopolymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000012041 precatalyst Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920006029 tetra-polymer Polymers 0.000 description 1
- XBFJAVXCNXDMBH-UHFFFAOYSA-N tetracyclo[6.2.1.1(3,6).0(2,7)]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2CC1 XBFJAVXCNXDMBH-UHFFFAOYSA-N 0.000 description 1
- 238000006478 transmetalation reaction Methods 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present disclosure relates to a process for preparing an alpha-substituted acrylate, the process comprising: a) combining starting materials comprising an alpha- (halometh) acrylate and an organoaluminum compound, thereby forming a product comprising the alpha-substituted acrylate.
Description
Cross Reference to Related Applications
This application claims priority from U.S. application No. 62/954,956 filed on 30.12.2019, which is incorporated herein by reference in its entirety.
Background
Alpha-substituted acrylates, such as alpha- (alkyl) acrylates or alpha- (polymer-based) acrylates, are important intermediates for the preparation of useful polymeric materials. Synthetic routes to alpha-substituted acrylates and diacrylates from organozinc reagents are known in the art. However, such routes employ a metal exchange reaction (transmetalation) of an organozinc compound to an organocopper compound, and a direct reaction of an organoaluminum compound with a halogenated methacrylate is not known. The present disclosure addresses this need by demonstrating the direct reaction of organoaluminum compounds with α - (halomethyl) acrylates to synthesize α - (alkyl) and α - (polymer-based) acrylates.
Disclosure of Invention
The present disclosure relates to a process for preparing an alpha-substituted acrylate, the process comprising:
a) a combination of starting materials comprising an alpha- (halomethyl) acrylate and an organoaluminum compound,
thereby forming a product comprising an alpha-substituted acrylate.
Drawings
Fig. 1A and 1B provide NMR spectra of example 1.
Fig. 2A and 2B provide NMR spectra of example 2.
Detailed Description
Definition of
All references herein to the periodic table of elements shall refer to the periodic table of elements published and copyrighted in 2003 by CRC publishing company (CRC Press, Inc.). Moreover, any reference to one or more groups shall be to the group or groups reflected in this periodic table of the elements using the IUPAC system to number groups.
All parts and percentages are by weight unless stated to the contrary, implied by context, or customary in the art.
For purposes of united states patent practice, any patent, patent application, or publication mentioned herein is hereby incorporated by reference in its entirety (or the equivalent us version thereof is so incorporated by reference), especially with respect to the disclosure of synthetic techniques, definitions (where not inconsistent with any definitions provided herein) and general knowledge in the art.
The numerical ranges disclosed herein include all values from the lower value to the upper value and include the lower value and the upper value. For ranges containing an exact value (e.g., 1 or 2, or 3 to 5, or 6, or 7), any subrange between any two exact values is included (e.g., 1 to 2; 2 to 6; 5 to 7; 3 to 7; 5 to 6; etc.). Numerical ranges disclosed herein further encompass any fractional number between any two exact values.
The terms "comprising", "including", "having" and derivatives thereof are not intended to exclude the presence of any additional component, step or procedure, whether or not the component, step or procedure is specifically disclosed. Rather, the term "consisting essentially of …" excludes any other components, steps, or procedures from any subsequently recited range, except for components, steps, or procedures not essential to operability. The term "consisting of …" excludes any component, step or procedure not specifically recited or listed. Unless stated otherwise, the term "or" means the members listed individually as well as in any combination.
As used herein, the terms "hydrocarbyl", "hydrocarbyl group", and the like refer to compounds composed entirely of hydrogen and carbon, including aliphatic, aromatic, acyclic, cyclic, polycyclic, branched, unbranched, saturated, and unsaturated compounds. The terms "hydrocarbyl", "hydrocarbyl group", "alkyl group", "aryl group", and similar terms are intended to encompass each possible isomer, including each structural isomer or stereoisomer.
The term "cyclic" refers to a series of atoms in a polymer or compound, where such series contains one or more rings. Thus, the term "cyclic hydrocarbyl" refers to a hydrocarbyl group containing one or more rings. As used herein, "cyclic hydrocarbyl" may contain non-cyclic (straight or branched chain) moieties in addition to one or more rings.
"transfer metallization" or "metal exchange reaction" refers to organometallic reactions that involve the transfer of ligands from one metal to another.
The term "catalyst" may be used interchangeably with "procatalyst", "precatalyst", "procatalyst", "transition metal catalyst", "transition metal procatalyst", "polymerization catalyst", "polymerization procatalyst", "transition metal complex", "transition metal compound", "metal complex", "metal compound", "complex", "metal-ligand complex" and similar terms.
"cocatalyst" refers to a compound that can activate certain procatalysts to form an active catalyst capable of polymerizing unsaturated monomers. The term "cocatalyst" may be used interchangeably with "activator" and similar terms.
"active catalyst," "active catalyst composition," and similar terms refer to a transition metal compound that is capable of polymerizing unsaturated monomers with or without a cocatalyst. The active catalyst may be a "procatalyst" that becomes active to polymerize unsaturated monomers without a cocatalyst. Alternatively, the active catalyst may be a "procatalyst" which becomes active in combination with a cocatalyst to polymerize unsaturated monomers.
The term "polymer" refers to a substance prepared by reacting (i.e., polymerizing) a set of monomers, wherein the set of monomers is a set of monomers that are homogeneous (i.e., only one type) or a set of monomers that are heterogeneous (i.e., more than one type). The term polymer as used herein encompasses the term "homopolymer" which refers to a polymer prepared from a homogeneous set of monomers, and the term "interpolymer" as defined below.
The term "interpolymer" refers to a polymer prepared by polymerizing at least two different types of monomers. The term includes "copolymers," i.e., polymers prepared from two different types of monomers, as well as polymers prepared from more than two different types of monomers, such as terpolymers, tetrapolymers, etc. The term also includes all forms of interpolymers, such as random, block, homogeneous, heterogeneous, and the like.
"polyolefin" is a polymer produced by the polymerization of an olefin as a monomer, wherein the olefin monomer is a linear, branched or cyclic compound of carbon and hydrogen having at least one double bond. Thus, the term "polyolefin" as used herein encompasses and encompasses the terms "ethylene-based polymer", "propylene-based polymer", "ethylene homopolymer", "propylene homopolymer", "ethylene/a-olefin interpolymer", "ethylene/a-olefin copolymer", "ethylene/a-olefin multi-block interpolymer", "block composite", "designated block composite", "crystalline block composite", and "propylene/a-olefin interpolymer" and "propylene/a-olefin copolymer".
An "ethylene-based polymer" is a polymer that contains a majority amount of polymerized ethylene, by weight of the polymer, and optionally may further contain polymerized units of at least one comonomer. A "vinyl interpolymer" is an interpolymer that comprises, in polymerized form, a majority amount of ethylene, based on the weight of the interpolymer, and further comprises polymerized units of at least one comonomer. An "ethylene homopolymer" is a polymer comprising repeating units derived from ethylene but not excluding residual amounts of other components.
As used herein, the term "ethylene/a-olefin interpolymer" refers to a polymer comprising, in polymerized form, a majority weight percent of ethylene (based on the weight of the interpolymer), and at least one comonomer that is an a-olefin. The ethylene/a-olefin interpolymer may be a random or block interpolymer. The term "ethylene/a-olefin interpolymer" encompasses the terms "ethylene/a-olefin copolymer" and "ethylene/a-olefin multiblock interpolymer".
As used herein, the term "ethylene/a-olefin copolymer" refers to a copolymer comprising, in polymerized form, a majority weight percent of ethylene (based on the weight of the copolymer) and a comonomer that is an a-olefin, wherein ethylene and a-olefin are the only two monomer types. The ethylene/alpha-olefin copolymer may be a random or block copolymer.
As used herein, the term "ethylene/α -olefin multi-block interpolymer" or "olefin block copolymer" refers to an interpolymer comprising ethylene and one or more copolymerizable α -olefin comonomers in polymerized form, characterized by multiple blocks or segments of two or more (preferably three or more) polymerized monomer units, which blocks or segments differ in chemical or physical properties. In particular, this term refers to polymers comprising two or more (preferably three or more) chemically distinct regions or segments (referred to as "blocks") joined in a linear manner rather than in a pendent or grafted manner, i.e., polymers comprising chemically distinct units joined end-to-end (covalently bonded) relative to a polymeric functional group. Blocks differ in the amount or type of comonomer incorporated therein, density, amount of crystallinity, type of crystallinity (e.g., polyethylene versus polypropylene), crystallite size attributable to a polymer of such composition, type or degree of tacticity (isotactic or syndiotactic), regioregularity or regioirregularity, amount of branching (including long chain branching or hyper-branching), homogeneity, and/or any other chemical or physical property. The block copolymers are characterized by a unique distribution of both polymer polydispersity (PDI or Mw/Mn) and block length distribution, for example, based on the effect of using one or more shuttling agents in combination with the catalyst system. Non-limiting examples of olefin block copolymers of the present disclosure and methods for making the same are disclosed in U.S. Pat. nos. 7,858,706B 2, 8,198,374B 2, 8,318,864B 2, 8,609,779B 2, 8,710,143B 2, 8,785,551B 2, and 9,243,090B 2, all of which are incorporated herein by reference in their entirety.
The term "block composite" ("BC") refers to a polymer comprising three polymer components: (i) a vinyl polymer (EP) (soft copolymer) having an ethylene content of 10 to 90 mol% based on the total number of moles of polymerized monomer units in the vinyl polymer (EP); (ii) an alpha-olefin-based polymer (AOP) (hard copolymer) having an alpha-olefin content of greater than 90 mole percent based on the total moles of polymerized monomer units in the alpha-olefin-based polymer (AOP); and (iii)
A block copolymer (eblock copolymer) having an Ethylene Block (EB) and an α -olefin block (AOB); wherein the ethylene block of the block copolymer has the same composition as the EP of component (i) of the block composite and the α -olefin block of the block copolymer has the same composition as the AOP of component (ii) of the block composite. In addition, in block composites, the compositional split between the amount of EP and AOP will be substantially the same as the compositional split between the corresponding blocks in the block copolymer. Non-limiting examples of block composites of the present disclosure and methods for making the same are disclosed in U.S. patent nos. 8,686,087 and 8,716,400, which are incorporated herein by reference in their entirety.
The term "specified block composite" ("SBC") refers to a polymer that includes three polymer components: (i) a vinyl polymer (EP) (soft copolymer) having an ethylene content of 78 to 90 mol% based on the total number of moles of polymerized monomer units in the vinyl polymer (EP); (ii) an α -olefin-based polymer (AOP) (hard copolymer) having an α -olefin content of 61 to 90 mol% based on the total number of moles of polymerized monomer units in the α -olefin-based polymer (AOP); and (iii) a block copolymer (diblock copolymer) having an Ethylene Block (EB) and an α -olefin block (AOB); wherein the ethylene block of the block copolymer has the same composition as the EP of component (i) of the specified block composite and the α -olefin block of the block copolymer has the same composition as the AOP of component (ii) of the specified block composite. In addition, in a given block composite, the compositional split between the amounts of EP and AOP will be substantially the same as the compositional split between the corresponding blocks in the block copolymer. Non-limiting examples of specified block composites of the present disclosure and methods for making the same are disclosed in WO 2017/044547, which is incorporated herein by reference in its entirety.
The term "crystalline block composite" ("CBC") refers to a polymer comprising three components: (i) a crystalline vinyl polymer (CEP) having an ethylene content greater than 90 mole percent, based on the total moles of polymerized monomer units in the crystalline vinyl polymer (CEP); (ii) a crystalline alpha-olefin-based polymer (CAOP) having an alpha-olefin content of greater than 90 mole percent based on the total moles of polymerized monomer units in the crystalline alpha-olefin-based Copolymer (CAOP); and (iii) a block copolymer comprising a Crystalline Ethylene Block (CEB) and a crystalline alpha-olefin block (CAOB); wherein the CEB of the block copolymer is of the same composition as the CEP of component (i) of the crystalline block composite and the CAOB of the block copolymer is of the same composition as the CAOP of component (ii) of the crystalline block composite. In addition, in a crystalline block composite, the compositional split between the amounts of CEP and CAOP will be substantially the same as the compositional split between the corresponding blocks in the block copolymer. Non-limiting examples of crystalline block composites of the present disclosure and methods for making the same are disclosed in U.S. patent No. 8,822,598B2 and WO 2016/01028961 a1, which are incorporated herein by reference in their entirety.
A "propylene-based polymer" is a polymer that contains a majority amount of polymerized propylene, by weight of the polymer, and optionally may further contain polymerized units of at least one comonomer. A "propylene-based interpolymer" is an interpolymer that contains a majority amount of propylene, in polymerized form, based on the weight of the interpolymer, and further contains polymerized units of at least one comonomer. A "propylene homopolymer" is a polymer comprising repeating units derived from propylene, but does not exclude residual amounts of other components.
As used herein, the term "propylene/α -olefin interpolymer" refers to a polymer comprising, in polymerized form, a majority weight percent of propylene (based on the weight of the interpolymer), and at least one comonomer which is an α -olefin (where ethylene is considered an α -olefin). The propylene/α -olefin interpolymer may be a random or block interpolymer. The term "propylene/α -olefin interpolymer" includes the term "propylene/α -olefin copolymer".
As used herein, the term "propylene/α -olefin copolymer" refers to a copolymer comprising, in polymerized form, a majority weight percent of propylene (based on the weight of the copolymer) and a comonomer that is an α -olefin, where propylene and α -olefin are the only two monomer types. The propylene/α -olefin copolymer may be a random or block copolymer.
The terms "polymer group", "polymer group" and similar terms refer to a polymer lacking one hydrogen.
The terms "polyolefin group", "polyolefin group" and similar terms refer to polyolefins lacking one hydrogen.
Alpha- (halomethyl) acrylates
The starting material of step a) of the process of the present disclosure comprises an alpha- (halomethyl) acrylate. In certain embodiments, the α - (halomethyl) acrylate has the formula (II):
x is halogen; and is provided with
R1 is a C1-C30 hydrocarbyl group;
in certain embodiments, X is halogen and is selected from the group consisting of fluoride, chloride, bromide, and iodide.
In certain embodiments, R1 is a C1-C30 hydrocarbon group that may be linear, branched, or cyclic. In further embodiments, R1 is a C1-C30 alkyl group that may be linear, branched, or cyclic. For example, R1 can be a straight, branched, or cyclic alkyl group containing 1 to 30 carbon atoms, or 1 to 20 carbon atoms, or 1 to 10 carbon atoms, or 1 to 8 carbon atoms, or 1 to 3 carbon atoms.
Organic aluminum compound
The starting material of step a) of the process of the present disclosure comprises formula R 3 An organoaluminum compound of Al, wherein each R is independently a C1-C26 hydrocarbyl group or a polyolefin group.
In certain embodiments, formula (ilia) isR 3 Each R of the organoaluminum compound of Al is independently a C1-C26 hydrocarbyl group. In certain embodiments, formula R 3 Each R of the organoaluminum compounds of Al is independently a C1-C26 hydrocarbon group that may be linear, branched, or cyclic. In other embodiments, formula R 3 Each R of the organoaluminum compounds of Al is independently a C1-C26 alkyl group which may be linear, branched or cyclic. For example, of the formula R 3 Each R of the organoaluminum compounds of Al can independently be a linear, branched, or cyclic alkyl group containing 1 to 26 carbon atoms, or 1 to 10 carbon atoms, or 1 to 8 carbon atoms.
In some embodiments, formula R 3 Each R of the organoaluminum compounds of Al is independently a polyolefin group. In other embodiments, formula R 3 Each R of the organoaluminum compounds of Al is independently a polyolefin group, which can be defined by the property of R-H, wherein the number average molecular weight of R-H is greater than 365 g/mol. In other embodiments, formula R 3 Each R of the organoaluminum compounds of Al is independently a polyolefin group, which can be defined by the properties of R-H, wherein the number average molecular weight of R-H is greater than 365g/mol to 10,000,000g/mol, or greater than 365g/mol to 5,000,000g/mol, or greater than 365g/mol to 1,000,000g/mol, or greater than 365g/mol to 750,000g/mol, or greater than 365g/mol to 500,000g/mol, or greater than 365g/mol to 250,000 g/mol.
In other embodiments, formula R 3 Each R of the organoaluminum compound of Al is independently a polyolefin group, which can be defined by the properties of R-H, wherein the density of R-H is from 0.850g/cc to 0.965g/cc, or from 0.860g/cc to 0.950g/cc, or from 0.865g/cc to 0.925 g/cc.
In other embodiments, formula R 3 Each R of the organoaluminum compounds of Al is independently a polyolefin group, which can be defined by the properties of R-H, wherein the melt index (I2) of R-H is from 0.01 g/10 min to 2,000 g/10 min, or from 0.01 g/10 min to 1,500 g/10 min, or from 0.1 g/10 min to 1,000 g/10 min, or from 0.1 g/10 min to 500 g/10 min, or from 0.1 g/10 min to 100 g/10 min.
In other embodiments, formula R 3 Each R of the organoaluminum compound of Al is independentlyAnd is immediately a polyolefin group, which may be defined by the nature of R-H, wherein R-H has a number average molecular weight distribution (Mw/Mn or PDI) of from 1 to 10, or from 1 to 7, or from 1 to 5, or from 2 to 4.
In certain embodiments, formula R 3 Each R of the organoaluminum compound of Al is independently an ethylene homopolymer group comprising units derived from ethylene.
In certain embodiments, formula R 3 Each R of the organoaluminum compound of Al is independently an ethylene/α -olefin interpolymer radical comprising units derived from ethylene and at least one C3 to C30 α -olefin. The C3-C30 alpha-olefin may be, for example, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, or 1-octadecene.
In certain embodiments, formula R 3 Each R of the organoaluminum compound of Al is independently an ethylene/α -olefin copolymer base comprising units derived from ethylene and a C3-C30 α -olefin. The C3-C30 alpha-olefin may be, for example, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene or 1-octadecene.
In certain embodiments, formula R 3 Each R of the organoaluminum compound of Al is independently an ethylene/α -olefin multi-block interpolymer radical or an olefin block copolymer radical, as defined herein.
In other embodiments, formula R 3 Each R of the organoaluminum compound of Al is independently a polymer base of a block composite, a specified block composite, or a crystalline block composite, as defined herein.
In certain embodiments, formula R 3 Each R of the organoaluminum compounds of Al is independently a propylene homopolymer group comprising units derived from propylene.
In certain embodiments, formula R 3 Each R of the organoaluminum compounds of Al is independently a propylene/α -olefin interpolymer group comprising units derived from propylene and at least one comonomer which is ethylene or a C3-C30 α -olefin. The C3-C30 alpha-olefin may be, for example, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodeceneTetraene, 1-hexadecene or 1-octadecene.
In certain embodiments, formula R 3 Each R of the organoaluminum compounds of Al is independently a propylene/α -olefin copolymer radical comprising units derived from propylene and a comonomer which is ethylene or a C3-C30 α -olefin. The C3-C30 alpha-olefin may be, for example, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene or 1-octadecene.
To the formula R 3 An embodiment in which each R of the organoaluminum compound of Al is independently a polyolefin group, formula R 3 The organoaluminum compound of Al can be prepared by process (a1), wherein process (a1) comprises combining starting materials comprising:
i) an olefin monomer component;
ii) a catalyst; and is
iii) formula J 3 A chain shuttling agent for Al, wherein each J is independently a C1-C20 hydrocarbyl group,
thereby forming a compound comprising the formula R 3 A solution or slurry of an organoaluminum compound of Al.
The starting materials i) the olefin monomer component comprises one or more olefin monomers. Suitable olefin monomers comprise linear or branched alpha-olefins of 2 to 30 carbon atoms, alternatively 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene; cyclic olefins of 3 to 30, alternatively 3 to 20 carbon atoms such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene and 2-methyl-1, 4,5, 8-dimethanol-1, 2,3,4,4a,5,8,8 a-octahydronaphthalene. Suitable olefin monomers are disclosed, for example, in U.S. Pat. No. 7,858,706 at column 16, lines 5-36 and U.S. Pat. No. 12 at column 7-41 of 8,053,529, both of which are incorporated herein by reference. In certain embodiments, the starting material i) may comprise ethylene and optionally one or more olefin monomers other than ethylene, such as propylene or 1-octene.
With respect to the starting material ii), suitable catalysts comprise any compound or combination of compounds suitable for preparing a polymer of the desired composition or type. One or more catalysts may be used. For example, the first and second olefin polymerization catalysts may be used to prepare polymers that differ in chemical or physical properties. Both heterogeneous and homogeneous catalysts may be employed. Examples of heterogeneous catalysts include Ziegler-Natta compositions, especially group 4 metal halides supported on group 2 metal halides or mixed halides and alkoxides, and chromium or vanadium based catalysts. Alternatively, for ease of use and to produce narrow molecular weight polymer fragments in solution, the catalyst may be a homogeneous catalyst comprising an organometallic compound or metal complex, such as a compound or complex based on a metal selected from groups 3-15 or the lanthanide series of the periodic table of elements. The starting materials ii) may comprise a cocatalyst in addition to the catalyst. The cocatalyst can be a cation forming cocatalyst, a strong Lewis Acid (Lewis Acid), or a combination thereof. Suitable catalysts and co-catalysts are disclosed, for example, in U.S. Pat. No. 7,858,706 at column 19, line 45 to column 51, line 29, and at column 16, line 37 to column 48, line 17 of U.S. Pat. No. 8,053,529, which are incorporated herein by reference. Suitable procatalysts that may also be added include, but are not limited to, PCT publications WO 2005/090426, WO 2005/090427, WO 2007/035485, WO 2009/012215, WO 2014/105411, WO 2017/173080; those disclosed in U.S. patent publication nos. 2006/0199930, 2007/0167578, 2008/0311812 and 7,355,089B 2, 8,058,373B 2 and 8,785,554B 2.
With respect to the starting material iii), the chain shuttling agent has the formula J 3 Al, wherein each J is independently a hydrocarbyl group having 1 to 20 carbon atoms. The hydrocarbyl group of J has 1 to 20 carbon atoms, alternatively 2 to 12 carbon atoms. The hydrocarbyl group of J may be an alkyl group, which may be straight or branched. J may be an alkyl group exemplified by ethyl, propyl, octyl, and combinations thereof. Suitable chain shuttling agents include trialkylaluminum compounds, such as triethylaluminum. Suitable chain shuttling agents are described at column 16, line 37 to column 19, line 44 of U.S. Pat. No. 7,858,706, and U.S. Pat. No. 7,8588,053,529 from column 12, line 49 to column 14, line 40, both of which are incorporated herein by reference.
For the preparation of the formula R 3 The starting materials for the organoaluminum compound of Al may optionally further comprise one or more additional starting materials selected from the group consisting of: iv) a solvent, vi) a scavenger, vii) an adjuvant and viii) a polymerization aid. Toluene and Isopar TM E is an example of a solvent for the starting material iv). Isopar TM E is an isoparaffin fluid, typically containing less than 1ppm benzene and less than 1ppm sulfur, commercially available from ExxonMobil Chemical Company.
For the preparation of the formula R 3 Process conditions and equipment for organoaluminum compounds of Al are known in the art and are disclosed, for example, in U.S. patent No. 7,858,706 and U.S. patent No. 8,053,529, which are incorporated herein by reference. For example, process (a1) may be characterised by polymerisation, which is desirably carried out as a continuous polymerisation, preferably a continuous solution polymerisation, in which the catalyst component, shuttling agent, monomer and optional solvents, adjuvants, scavengers and polymerisation aids are continuously supplied to a reaction zone and polymer product is continuously removed from the reaction zone. Within the scope of the term "continuous" as used in this context are those methods in which reactants are added intermittently and products are removed at less regular or irregular intervals so that over time the overall process is substantially continuous.
The polymerization can be advantageously used as a high pressure, solution, slurry or gas phase polymerization process. For solution polymerization processes, it is desirable to employ a homogeneous dispersion of the catalyst component in a liquid diluent in which the polymer is soluble under the polymerization conditions employed. In us patent No. 5,783,512 a process is disclosed for producing such homogeneous catalyst dispersions using very fine silica or similar dispersants, where the solubility of the metal complex or cocatalyst is poor. The solution process, especially the continuous solution process, for preparing the novel polymers of the present invention is preferably carried out at a temperature between 80 ℃ and 250 ℃, more preferably between 100 ℃ and 210 ℃ and most preferably between 110 ℃ and 210 ℃. High pressure processes are typically carried out at temperatures of from 100 ℃ to 400 ℃ and pressures above 500 bar (50 MPa). Slurry processes typically use an inert hydrocarbon diluent and are at a temperature of from 0 ℃ to just below the temperature at which the resulting polymer becomes substantially soluble in the inert polymerization medium. The preferred temperature in the slurry polymerization is 30 ℃, preferably 60 ℃, up to 115 ℃, preferably up to 100 ℃. The pressure is typically in the range of atmospheric pressure (100kPa) to 500psi (3.4 MPa).
Preparation of alpha-substituted acrylic acid esters
The process involves the preparation of alpha-substituted acrylates. In certain embodiments, the α -substituted acrylate has the formula (I):
wherein R is C1-C26 alkyl or polyolefin group; and is
R1 is a C1-C30 hydrocarbyl group;
each of the R and R1 groups of the alpha-substituted acrylate of formula (I) is independently of the formula R 3 All embodiments of the R group of the organoaluminum compound of Al and the R1 group of the α - (halomethyl) acrylate of formula (II) are the same and include all embodiments thereof. In fact, the disclosed methods involve nucleophilic substitution reactions wherein X, halogen is represented by formula R 3 R-substituted leaving group of organoaluminum compound of Al.
In certain embodiments, step a) of the methods of the present disclosure may be performed simply. In further embodiments, the starting material in step a) of the process of the present disclosure further comprises a hydrocarbon solvent. In further embodiments, the starting material in step a) of the process of the present disclosure further comprises a hydrocarbon solvent that is a non-aromatic hydrocarbon solvent.
In some embodiments, step a) of the methods of the present disclosure is performed at a temperature above the melting temperature of the R group as defined herein. For example, but not limited to, step a) of the method of the present disclosure may be performed at a temperature of 15 ℃ to 100 ℃.
In some embodiments, in step a), the α - (halomethyl) acrylate is reacted with a compound of formula R 3 The ratio of the organoaluminum compound of Al is 15:1, or 12:1, or 9:1, or 6:1, or 3:1, or 2:1, or 1: 1.
In preferred embodiments, the methods of the present disclosure exclude any metal exchange step or reaction.
In certain embodiments, step a) of the methods of the present disclosure is non-catalytic. In further embodiments, step a) of the methods of the present disclosure may be catalyzed by one or more organic catalysts. An organic catalyst is a catalyst excluding any metallic elements. Thus, in certain embodiments, the starting material in step a) of the present process further comprises an organic catalyst. For example, the starting material in step a) of the process of the present disclosure also includes a nitrogen-containing heterocycle as disclosed in WO 2019/182992. The nitrogen-containing heterocycle may be, for example, but is not limited to, N-methylimidazole.
Specific embodiments of the present disclosure include, but are not limited to, the following:
1. a process for preparing an alpha-substituted acrylate, the process comprising:
a) combining starting materials comprising an alpha- (halometh) acrylate and an organoaluminum compound, thereby forming a product comprising the alpha-substituted acrylate.
2. A process for preparing an alpha-substituted acrylate, the process comprising:
a) the combination comprising an alpha- (halomethyl) acrylate and a compound of formula R 3 Starting materials for the organoaluminum compound of Al,
thereby forming a product comprising the α -substituted acrylate, wherein:
the alpha-substituted acrylate has the formula (I):
the α - (halomethyl) acrylate has the formula (II):
each R is independently a C1-C26 hydrocarbyl group or a polyolefin group;
each R1 is independently a C1-C30 hydrocarbyl group; and is
X is halogen.
i. The process of embodiment 1 or embodiment 2, wherein the starting material of step a) further comprises a solvent.
4. The method of embodiment 3, wherein the solvent is a non-aromatic hydrocarbon solvent.
5. The method of any one of the preceding embodiments, wherein the method excludes any metal exchange step or reaction.
6. The process according to any one of the preceding embodiments, wherein the starting material of step a) further comprises an organic catalyst.
7. The method of embodiment 6, wherein the organic catalyst is a nitrogen-containing heterocycle.
8. The method of embodiment 7, wherein the nitrogen-containing heterocycle is N-methylimidazole.
9. The method of any one of the preceding embodiments, wherein each R1 is independently a linear, branched, or cyclic C1-C30, or C1-C10, or C1-C8, or C1-C3 alkyl group.
10. The method of any one of the preceding embodiments, wherein each R is independently a C1-C30 hydrocarbyl group.
11. The method of embodiment 10, wherein each R is independently a linear, branched, or cyclic C1-C30, or C1-C10, or C1-C8 alkyl.
12. The method of any one of embodiments 1 to 9, wherein each R is independently a polyolefin group.
13. The method of embodiment 12, wherein the polyolefin group is a vinyl polymer group.
14. The method of embodiment 13, wherein the polyolefin group is an ethylene homopolymer group comprising units derived from ethylene.
15. The process of embodiment 13 wherein the polyolefin group is an ethylene/a-olefin interpolymer group comprising units derived from ethylene and a C3-C30 a-olefin.
16. The process of embodiment 13 wherein the polyolefin group is an ethylene/a-olefin copolymer group comprising units derived from ethylene and a C3-C30 a-olefin.
17. The process of embodiment 15 or 16 wherein the C3-C30 a-olefin is selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene.
18. The process of embodiment 13 wherein the polyolefin group is an ethylene/a-olefin multi-block interpolymer group.
19. The method of embodiment 13, wherein the polyolefin group is selected from the group consisting of a polymer group of a block composite, a polymer group of a specified block composite, and a polymer group of a crystalline block composite.
20. The method of embodiment 12, wherein the polyolefin group is a propylene-based polymer group.
21. The method of embodiment 20, wherein the polyolefin group is a propylene homopolymer group comprising units derived from propylene.
22. The process of embodiment 20 wherein the polyolefin group is a propylene/α -olefin interpolymer group comprising units derived from propylene and ethylene or a C4-C30 α -olefin.
23. The method of embodiment 20, wherein the polyolefin group is a propylene/α -olefin copolymer group comprising units derived from propylene and ethylene or a C4-C30 α -olefin.
24. The process of embodiment 22 or 23 wherein the C4-C30 a-olefin is selected from the group consisting of 1-butene, 1-hexene, and 1-octene.
25. The method of any one of embodiments 12 to 24, wherein the polyolefin group can be defined by the nature of R-H, and wherein the number average molecular weight of R-H is greater than 365 g/mol.
26. The process of any one of embodiments 12 to 25 wherein the polyolefin group can be defined by the nature of R-H, and wherein the number average molecular weight of R-H is from greater than 365g/mol to 10,000,000g/mol, or from greater than 365g/mol to 5,000,000g/mol, or from greater than 365g/mol to 1,000,000g/mol, or from greater than 365g/mol to 750,000g/mol, or from greater than 365g/mol to 500,000g/mol, or from greater than 365g/mol to 250,000 g/mol.
27. The method of any of embodiments 12 to 26, wherein the polyolefin group can be defined by the properties of R-H, and wherein the density of R-H is from 0.850g/cc to 0.965g/cc, or from 0.860g/cc to 0.950g/cc, or from 0.865g/cc to 0.925 g/cc.
28. The method of any of embodiments 12 to 27, wherein the polyolefin group can be defined by the properties of R-H, and wherein the melt index (I2) of R-H is from 0.01 g/10 min to 2,000 g/10 min, or from 0.01 g/10 min to 1,500 g/10 min, or from 0.1 g/10 min to 1,000 g/10 min, or from 0.1 g/10 min to 500 g/10 min, or from 0.1 g/10 min to 100 g/10 min.
29. The method of any of embodiments 12 to 28, wherein the polyolefin group can be defined by the nature of R-H, and wherein the number average molecular weight distribution (Mw/Mn) of R-H is from 1 to 10, or from 1 to 7, or from 1 to 5, or from 2 to 4.
30. The method according to any one of the preceding embodiments, wherein step a) is performed at a temperature of from 15 ℃ to 100 ℃.
31. The process according to any one of the preceding embodiments, wherein in step a) the ratio of the a- (halometh) acrylate to the organoaluminum compound is 15:1, or 12:1, or 9:1, or 6:1, or 3:1, or 2:1, or 1: 1.
32. The process of embodiment 1, wherein the organoaluminum compound is prepared by a process comprising combining starting materials comprising:
i) an olefin monomer component; ii) a catalyst; and iii) a chain shuttling agent, thereby forming a solution or slurry comprising the organoaluminum compound.
33. The method according to any one of embodiments 2 to 31, wherein the method is performed by a packPreparation of formula R by a process comprising combining starting materials 3 The organoaluminum compound of Al, the starting materials comprising:
i) an olefin monomer component; ii) a catalyst; and iii) a chain shuttling agent of the formula J3Al, wherein each J is independently a C1-C20 hydrocarbon group,
thereby forming a solution or slurry comprising the organoaluminum compound of formula R3 Al.
Test method
Density:
density is measured according to ASTM D-792, method B.
Melt index:
melt index (I) was measured according to ASTM D-1238 (incorporated herein by reference in its entirety), condition 190 ℃/2.16kg 2 ) And reported as grams eluted every 10 minutes.
GPC：
The properties of the sample polymers were tested by GPC according to the following.
Molecular Weight (MW) and Molecular Weight Distribution (MWD) determinations were performed using a high temperature gel permeation chromatography system (GPC IR) consisting of an infrared concentration detector (IR-5) from percoll moker Inc (PolymerChar Inc) (Valencia, Spain). The carrier solvent is 1,2, 4-Trichlorobenzene (TCB). The autosampler chamber was operated at 160 ℃ and the column chamber was operated at 150 ℃. The columns used were four Polymer Laboratories (Polymer Laboratories) Mixed a LS, 20 micron columns. The chromatographic solvent (TCB) and the sample preparation solvent were from the same solvent source with 250ppm of Butylated Hydroxytoluene (BHT) and nitrogen sparge. Samples were prepared in TCB at a concentration of 2 mg/mL. The polymer sample was gently shaken at 160 ℃ for 2 hours. The injection volume was 200 μ l and the flow rate was 1.0 ml/min.
The GPC column set was calibrated with 21 narrow molecular weight distribution polystyrene standards. The molecular weights of the standards range from 580 grams per mole to 8,400,000 grams per mole (g/mol) and are arranged in 6 "cocktail" mixtures with at least a decimal separation between the individual molecular weights.
The GPC column set was calibrated before running the examples by running twenty-one narrow molecular weight distribution polystyrene standards. The molecular weight (Mw) of the standards ranged from 580 grams per mole to 8,400,000 grams per mole (g/mol) and the standards were contained in 6 "cocktail" mixtures. Each standard mixture is at least a decade apart between individual molecular weights. The standard mixtures were purchased from polymer laboratories (Shropshire, UK). The polystyrene standards were prepared as follows: for molecular weights equal to or greater than 1,000,000g/mol, 0.025g in 50mL of solvent; and for molecular weights less than 1,000,000g/mol, 0.05g in 50mL of solvent. The polystyrene standards were dissolved by gently stirring at 80 ℃ for 30 minutes. The narrow standards mixtures were run first and in order of decreasing highest molecular weight (Mw) components to minimize degradation. The polystyrene standard peak molecular weight was converted to polyethylene Mw using a Mark-Houwink constant. After obtaining the constants, these two values were used to construct two linear reference conventional calibration values for polyethylene molecular weight and polyethylene intrinsic viscosity as a function of the elution column.
The peak polystyrene standard molecular weight was converted to polyethylene molecular weight using the following equation (as described in Williams and Ward, journal of polymer science: polymer press (j.polym.sci., polym.let.), 6,621 (1968)):
M polyethylene (PE) ＝A(M Polystyrene ) B (1)
Here, the value of B was 1.0, and the experimentally measured value of a was about 0.41.
The corresponding polyethylene-equivalent calibration points obtained from equation (1) were fitted to their observed elution volumes of polystyrene standards using a third order polynomial.
The number average molecular weight, weight average molecular weight, and z average molecular weight were calculated according to the following equations:
wherein, Wf i Is the weight fraction of the ith component, and M i Is the molecular weight of the ith component.
MWD is expressed as the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn).
The exact value of a is determined by adjusting the value of a in equation (1) until the Mw calculated using equation (3) and the corresponding retention volume polynomial is consistent with the known value of Mw of 120,000g/mol referenced to a standard linear polyethylene homopolymer.
The GPC system consisted of Waters (Milford, Mass.) equipped with an onboard differential Refractometer (RI), a 150 ℃ high temperature chromatograph (other suitable high temperature GPC instruments include polymer laboratories model 210 and model 220, shirpurshire, uk). Additional detectors may include an IR4 infrared detector from pelithelix corporation (Polymer ChAR) (balun west spain), a precision detector (Amherst, Mass.), a dual angle laser scattering detector model 2040, and a wiskotek (Viscotek) (Houston, Tex, texas) 150R 4 capillary solution viscometer. GPC with the last two independent detectors and at least one of the first detectors is sometimes referred to as "3D-GPC," while the term "GPC" alone generally refers to conventional GPC. Depending on the sample, either a 15 degree angle or a 90 degree angle of the light scattering detector is used for calculation purposes.
Data collection was performed using the Viscotek TriSEC software version 3 and the 4-channel wisdom data manager DM 400. The system was equipped with an on-line solvent degasser from polymer laboratories (shoplipshire, uk). Suitable high temperature GPC columns may be used, such as four 30cm long Shodex HT 80313 micron columns or four 30cm Polymer Labs columns of 20 micron mixed pore size packing (MixA LS, Polymer laboratories). The sample carousel chamber was operated at 140 ℃ and the column chamber was operated at 150 ℃. The samples were prepared at a concentration of 0.1 grams of polymer in 50 milliliters of solvent. The chromatographic solvent and sample preparation solvent contained 200ppm of Butylated Hydroxytoluene (BHT). Both solvents were sparged with nitrogen. The polyethylene sample was gently stirred at 160 ℃ for four hours (4 hours). The injection volume was 200 microliters (μ L). The flow rate through GPC was set to 1 ml/min.
13 1 NMR (C and H):
NMR analysis was performed at room temperature using standard NMR solvents, such as chloroform or benzene, and data were acquired on a Varian 500MHz spectrometer.
GCMS：
Tandem gas chromatography/low resolution mass spectrometry using electron impact ionization (EI) was performed at 70eV on an Agilent Technologies 6890N series gas chromatograph equipped with Agilent Technologies 5975 inert XL mass selection detector and Agilent Technologies capillary column (HP1MS, 15m x 0.25mm, 0.25 micron) for the following:
the programming method comprises the following steps:
oven equilibration time of 0.5 min at 50 deg.C
Then 25 deg.C/min to 200 deg.C, and maintaining for 5min
Run time 11min
Examples
The following examples are intended to illustrate some embodiments of the invention and should not be construed as limiting the scope of the invention as set forth in the claims.
Unless otherwise indicated, all materials and reagents were commercially available, such as from Sigma Aldrich (Sigma Aldrich).
Example 1
The reaction of example 1 was carried out under an inert nitrogen atmosphere glove box and according to the above exemplary and non-limiting reaction scheme. To a 20mL vial of ethyl bromomethacrylate (193mg) in anhydrous methylcyclohexane (5mL) was slowly added Oct3Al solution (122.5mg, 0.33 eq) at room temperature. The reaction mixture turned light yellow and the color disappeared after overnight at room temperature. 1,3, 5-tribromobenzene (76mg, 0.244mmol) was added as an internal standard.
After 12 hours at room temperature, the NMR conversion was calculated to be about 35%, as seen in fig. 1A.
The reaction mixture was heated at 85 ℃ for an additional 6 hours. NMR showed about 60% conversion with some by-product formation, as seen in fig. 1B. Integration gave 61% NMR yield compared to internal standard. Further heating did not improve conversion while more by-products were formed.
Example 2
The reaction of example 2 was carried out under an inert nitrogen atmosphere glove box and according to the above exemplary and non-limiting reaction scheme. To a 20mL vial of methyl chloromethacrylate (134.6mg) in dry methylcyclohexane (5mL) was slowly added Oct3Al solution (136.5mg, 0.33 equiv) at room temperature. The reaction mixture turned light yellow and the color disappeared after overnight at room temperature. 1,3, 5-tribromobenzene (71.7mg, 0.227mmol) was added as an internal standard.
After 12 hours at room temperature, the NMR conversion was calculated to be about 39%, as seen in fig. 2A.
The reaction mixture was heated at 85 ℃ for an additional 6 hours. NMR showed about 56% conversion with some by-product formation, as seen in fig. 2B. Integration gives 46% NMR to 50% NMR yield compared to internal standard. Further heating did not improve conversion while more by-products were formed.
Claims (13)
1. A process for preparing an alpha-substituted acrylate, the process comprising:
a) the combination comprises an alpha- (halomethyl) acrylate and a compound of the formula R 3 Starting materials for the organoaluminum compound of Al,
thereby forming a product comprising the α -substituted acrylate, wherein:
the alpha-substituted acrylate has the formula (I):
the α - (halomethyl) acrylate has the formula (II):
each R is independently a C1-C26 hydrocarbon or polyolefin group;
each R1 is independently a C1-C30 hydrocarbyl group; and is
X is halogen.
2. The process of claim 1, wherein the starting material of step a) further comprises a solvent.
3. The method according to claim 2, wherein the solvent is a non-aromatic hydrocarbon solvent.
4. The method of any one of the preceding claims, wherein the method excludes any metal exchange step or reaction.
5. The process of any one of the preceding claims, wherein the starting material of step a) further comprises an organic catalyst.
6. The method of any one of the preceding claims, wherein each R is independently a C1-C26 hydrocarbyl group.
7. The process of any one of claims 1 to 5, wherein each R is independently a polyolefin group that can be defined by the nature of R-H, and wherein the number average molecular weight of R-H is greater than 365 g/mol.
8. The method of claim 7, wherein the polyolefin group is a vinyl polymer group.
9. The process of claim 8 wherein the polyolefin group is an ethylene homopolymer group comprising units derived from ethylene.
10. The process of claim 8 wherein the polyolefin group is an ethylene/a-olefin interpolymer group comprising units derived from ethylene and a C3-C30 a-olefin.
11. The method of claim 7, wherein the polyolefin group is a propylene-based polymer group.
12. The process of claim 11 wherein the polyolefin group is a propylene homopolymer group comprising units derived from propylene.
13. The process of embodiment 11 wherein the polyolefin group is a propylene/α -olefin interpolymer group comprising units derived from propylene and ethylene or a C4-C30 α -olefin.
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| US62/954956 | 2019-12-30 | ||
| PCT/US2020/065764 WO2021138073A1 (en) | 2019-12-30 | 2020-12-17 | Process for preparing an alpha-substituted acrylate |
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| DE102009028939A1 (en) * | 2009-08-27 | 2011-03-03 | Ludwig-Maximilians-Universität München | Process for the preparation of arylaluminum halides and their use |
| US20140249286A1 (en) * | 2004-03-17 | 2014-09-04 | Dow Global Technologies Llc | Catalyst Composition Comprising Shuttling Agent for Ethylene Multi-Block Copolymer Formation |
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| US5783512A (en) | 1996-12-18 | 1998-07-21 | The Dow Chemical Company | Catalyst component dispersion comprising an ionic compound and solid addition polymerization catalysts containing the same |
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| US7355089B2 (en) | 2004-03-17 | 2008-04-08 | Dow Global Technologies Inc. | Compositions of ethylene/α-olefin multi-block interpolymer for elastic films and laminates |
| BRPI0508173B1 (en) | 2004-03-17 | 2016-03-15 | Dow Global Technologies Inc | multiblock copolymers, polymer, copolymer, a functional derivative, homogeneous polymer blend, process for preparing a propylene-containing multiblock copolymer and process for preparing a 4-methyl-1-pentene multiblock copolymer |
| TWI426089B (en) | 2005-09-15 | 2014-02-11 | Dow Global Technologies Llc | Catalytic olefin block copolymers with controlled block sequence distribution |
| MX2008014671A (en) | 2006-05-17 | 2009-01-26 | Dow Global Technologies Inc | High efficiency solution polymerization process. |
| CN101855078B (en) | 2007-07-13 | 2014-08-27 | 陶氏环球技术有限责任公司 | Ethylene/alpha-olefin interpolymers containing low crystallinity hard blocks |
| US8716400B2 (en) | 2009-10-02 | 2014-05-06 | Dow Global Technologies Llc | Block composites and impact modified compositions |
| US8822599B2 (en) | 2010-06-21 | 2014-09-02 | Dow Global Technologies Llc | Crystalline block composites as compatibilizers |
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| JP6802151B6 (en) | 2014-08-21 | 2021-01-20 | ダウ グローバル テクノロジーズ エルエルシー | Hot melt adhesive composition containing crystalline block composite |
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